Resins of poly(epoxyalkyl-2-oxazolidinone), phenolic based polyepoxides and monoepoxy compounds



United States Patent 3,413,377 RESINS OF POLY(EPOXYALKYL-2-OXAZOLIDI-NONE), PHENOLIC BASED POLYEPOXIDES AND MONOEPOXY COMPOUNDS Charles H.Schramm and Morris Zief, Easton, Pa., assignors to J. T. Baker ChemicalCompany, Phillipsburg, N.J., a corporation of New Jersey No Drawing.Continuation-impart of application Ser. N0. 515,439, Dec. 21, 1965. Thisapplication Apr. 28, 1966, Ser. No. 545,874

Claims. (Cl. 260-830) ABSTRACT OF THE DISCLOSURE Polymerizablecompositions may be prepared from polyepoxyoxazolidinone of the formulawherein A is a divalent hydrocarbon having 4 to 12 C, Z is an alkylenegroup of 1 to 18 C, divalent polyalkylene, or chloro-substitutedpolyoxyalkylene.

These polyepoxyoxazolidinones are reacted with polyglycidyl ethers ofpolyhydric phenols, and monoepoxy flexibilizers.

From 0.2 to 4 pts. of the polyepoxyoxazolidinone is used for each pt. ofthe polyglycidyl ether, and 3% to 70% of the monoepoxy flexi'bilizer isused based on the total of the other 2 components.

Oxazolidinone diepoxides may be prepared from the reaction ofpolypropylene glycol, and epichlorohydrin, followed by further reactionwith toluene diisocyanate.

This application is a continuation-in-part of our copending applicationSer. No. 515,439, filed on Dec. 21, 1965, now abandoned.

This invention relates to novel polymers. More particularly it relatesto novel polymers prepared by polymerizing a mixture containing apolyepoxyoxazolidinone, a phenolic based polyepoxide, and a monoepoxycompound.

Conventional phenolic based polyepoxide resins are rigid systems whichpossess low flexibility and little elongation. Various additives such asplasticizers, flexibilizers and other diluents have been used to improvethe flexibility and elongation of the phenolic based polyepoxycompounds. However, these additives produce various shortcomings in thephysical and chemical properties of the polymers.

Polyepoxyoxazolidinones, also referred to as polyepoxyoxazolidones, canbe admixed with the phenolic type resins to produce polymers having goodphysical and chemical properties. Notwithstanding the desirable physicaland chemical properties of such polymers, there is a need for additivesto provide additional desired properties, including increasedflexibility and elongation, with little or no loss of tensile strength.Various diluents, plasticizers or flexibilizers, when added to a mixtureof the phenolic based polyepoxides and polyepoxyoxazolidi nones areunsatisfactory in providing desirable properties in the cured mixtures.Some of the additives give little or no increased elongation whereasothers, although providing increased elongation, adversely affect otherproperties of the polymers.

It has now been found that polymers prepared from mixtures containing aphenolic based polyepoxide, a poly- (epoxyalkyl-Z-oxazolidinone), and amonoepoxy flexibilizer have many desirable physical and chemicalproperties including improved elongation with little loss in otherdesirable physical and chemical properties. The use ofv certain classesof the monoepoxy flexibilizers gives polymers with increased elongationwhile other physical and chemical properties of the polymers remainsubstan tially the same, and in some instances, better than the phenolicbased polyepoxide-polyepoxyoxazolidinone polymers without thefiexibilizer. Advantageous properties of the novel mixtures and polymersinclude: reduced viscosity of the monomeric mixture; whereas thepolymers show increased elongation with little sacrifice in tensilestrength, decreased water absorption, retention of high flexibility andgood tensile strength on heat aging of the polymers, good impactresistance, abrasion resistance, and good cohesive and adhesiveproperties.

Polyepoxyoxazolidinones are described in the literature, e.g., BelgianPatents 647,000 and 646,999, which were granted on Apr. 23, 1964. Theycan be prepared by reacting a polyisocyanate with a poly(halohydrin) ina quantity sufficient to provide two or more halohydrin groups perisocyanate group. The reaction can be conducted in the presence of acatalyst such as stannous octoate at temperatures ranging from about 15C. to C. to produce a poly(beta-halourethano) halohydrin which is thendehydrohalogenated, e.g., by use of 50% sodium hydroxide solution, toform the polyepoxyoxazolidinone.

The term polyisocyanate refers to compounds containing two or moreisocyanate (NCO) groups. The term polyhalohydrin refers to compoundscontaining two or more halohydrin groups wherein X is halogen. The termbeta-halourethano refers to the radical wherein X is halogen. The termepoxide or epoxy refers to the oxirane group f O Co The term residue inreference to organic polyisocyanates refers to the organic portion of apolyisocyanate compound exclusive of the reactive isocyanate groups.This term, as applied to polyisocyanates, indicates a polyvalentradical, e.g., tolylene, which was once part of a reactivepolyisocyanate which through one or more reactions makes up a part ofthe compound in question. The term residue in reference to apoly(halohydrin) refers to the organic portion of the poly(halohydrin)exclusive of the halohydrin groups.

Polyisocyanate reactants suitable for use in the preparation of thepolyepoxyoxazolidinones can be represented by the formula R(NCO) whereinn is an integer representing the number of isocyanate groups, e.g. 2 to4 but preferably 2, and R represents the organic residue of apolyisocyanate. This formula includes a wide variety of organicpolyisocyanates, including aromatic, aliphatic, and cycloaliphaticdiisocyanates and other polyisocyanates, Preferably the polyisocyanateresidue is a hydrocarbon having from about 4 to 12 carbon atoms, e.g.,alkylene, arylene such as phenylene or naphthalene, and alkylarylenesuch as tolylene. Representative polyisocyanates include: tolylene2,4-diisocyanate; m-phenylene diisocyanate; 4-chloro-1,3-phenylenediisocyanate; 4,4'-bisphenylene diisocyanate; diphenylmethane4,4'-diisocyanate; 1,5- naphthalene diisocyanate; 1,4tetramethylenediisocyanate; 1,6-hexamethylene diisocyanate; 1,10-decamethylenediisocyanate; 1,4-cyclohexylene diisocyanate; 4,4'methylenehis(cyclohexylisocyanate); 1,S-tetrahydronaphthalehe diisocyanate; andthe like. Commercial mixtures of tolylene-2,4-diisocyanate andtolylene-2,6-diisocyanate are preferred on the basis of economics.

Illustrative'of poly(halohydrin) reactants suitable for preparing thepolyepoxyoxazolidinones there can be mentioned:1,4-dich1orobutanediol-2,3; 1,4-dibromobutanediol 2,3; 2,3dichlorobutane diol 1,4; 2,3 dibromobutanediol 1,4; vinyl cyclohexanedichlorohydrin; epichlorohydrin adducts of various polyols includingglycerol, sorbitol, polyvinyl alcohol and poly(oxyalkylene) glycols suchas polyethylene glycol and polypropylene glycol. Preferably, thepoly(halohydrin) is an epichlorohydrin adduct of a poly(oxyalkyleneglycol) having from 2 to 4 carbon atoms in each alkylene chain, forexample an epichlorohydrin adduct of: polyethylene glycol; polypropyleneglycol; polybutylene glycol; and the like. Preferably, thepoly(oxyalkylene)glycols have molecular weights of about 100 to about3,000, and particularly from about 150 to 1,000. In preferredcompositions, the poly(halohydrin) will have a molecular weight of notgreater than 1,000 and will be a liquid.

Poly(epoxyoxazolidinones) employed in this invention can be representedby the formula wherein A is the organic residue of a polyisocyanate,e.g., tolylene; Z is an aliphatic group; n is an integer from 2 to 4 butpreferably 2; m is an integer from 1 to 3 but preferably 1, and either Yor Y is hydrogen and the remaining Y or Y represents a covalent bondconnecting the oxazolidone ring to Z. The aliphatic group as representedby Z can be selected from groups consisting of alkylene, substitutedalkylene, alkyleneoxy, cycloalkylene and substituted cycloalkylene andradicals made up of two or more of each of these groups or mixturesthereof. The alkylene, substituted alkylene, alkyleneoxy, cycloalkyleneand substituted cycloalkylene groups can have from 1 to about 18 carbonatoms in each of the groups, although these groups can be joined, e.g.the oxyalkylene portion of a poly(oxyalkylene)glycol, to form groupshaving molecular weights as high as 4,000 or more. Substituents on theabove recited substituted groups are preferably alkyl or halogen, e.g.,chloro. Preferably, the polyepoxyoxazolidinones employed in thisinvention are represented by the following formula:

II AN 0 CHgCH-CHz-(OR)n-OCH:CHCH2 2 wherein: A is the organic residue ofa diisocyanate;

R is a member selected from alkylene and chloro-substituted alkylenehaving from 1 to 4 carbon atoms, e.g.

kylene)glycol [H(OR),,OH] having a molecular weight of about 150 to1,000.

The phenolic based polyepoxides are preferably epichlorohydrin adductsof Bisphenol A, e.g., the diglycidyl ether of bis(4-hydroxyphenyl)dimethylmethane, although the diglycidyl ethers of resorcinol,hydroquinone, pyrocathechol, phloroglucinol, 4,4-dihydroxybiphenyl,4,4-dihydroxydiphenylsulfone may also be employed. In addition theglycidyl ethers of novolacs, such as Dows D.E.N. 438 epoxy novolacs, arealso useful. Preferably, the phenolic based polyepoxides are liquids,including highly viscous liquids at room temperature.

Broadly, the monoepoxy fiexibilizers are well known for fiexibilizingthe phenolic based polyepoxy resins. Illusstrative as suitable monoepoxyflexibilizers, there can be mentioned: the glycidyl ether of nonylphenol; the glycidyl ether of dodecyl phenol; phenol glycidyl ether;butyl glycidyl ether; monoglycidyl ethers of poly(oxyalkylene)- glycols,e.g., polyethylene glycol or polypropylene glycol having a molecularweight of about 150 to about 1,000 or more; and the glycidyl ether of analkanol having from 8 to 10 carbon atoms. In the case of themonoglycidyl ethers of poly(oxyalkylene) glycol flexibilizers, theflexibilizer molecule contains one epoxy group and one hydroxy group.Preferred monoepoxy flexibilizers can be represented by the formulawherein R is hydrocarbyl having from about 6 to 16 carbon atoms.Illustrative of R there can be mentioned aryl such as phenyl or naphthyland alkyl such as straight or branched chain octyl, decyl, and the like.Particularly preferred is the glycidyl ether of an alkanol having from 8to 10 carbon atoms and phenyl glycidyl ether.

The quantities of the various ingredients in the compositions of thisinvention can vary over a broad range. Illustratively, the ratio ofpolyepoxy compounds can vary from about 0.2 to 4 parts (by Weight) ofthe polyepoxyoxazolidinone per part of the phenolic based polyepoxideand preferably from about 0.3 to 1 part of the polyepoxyoxazolidinonefor each part of the phenolic based polyepoxide. The quantity of themonoepoxy flexibilizer can vary over a broad range such as that of fromabout 3% to 70% based on the total quantity (by weight) of thepolyoxazolidinone and phenolic based polyepoxide, preferably from about5% to 60% and particularly from about 15% to 45%, based on the totalquantity of polyepoxyoxazolidinone and phenolic based polyepoxide.

Conventional techniques are employed in preparing the resins of thisinvention. Thus, they can be prepared by the simple expediency of mixingtogether the various components at room temperature together with across-linking type of epoxy curing agent. Alternatively, the materialscan be mixed together and packaged and the curing agent added at thetime of use. Preferably, the curing agent is a polyfunctional amine, oran aliphatic polycarboxylic acid anhydride. The compositions cure atroom or elevated temperatures if a polyfunctional amine is employed asthe curing agent, whereas an anhydride curing agent generally requireselevated temperatures to effect the cure such as that of from about 70C. to C. The polyfunctional amine, i.e., an amine having at least twoactive amino hydrogen atoms which can be on the same nitrogen atom ordifferent nitrogen atoms is employed in amounts suflicient to providebetween about 0.2 and 4.0 amino hydrogen atoms per epoxy group of themixture, and preferably between 0.5 and 2.0 amino hydrogen atoms perepoxy group, although it is preferable to use the stoichiometricquantity of the polyfunctional amine required to react all the epoxygroups in the mixture. Suitable polyfunctional amines includemonoamines, diamines, triamines and higher polyamines such asZethylhexylamine; ,aniline; phenethylamine; cyclohexylamine;Z-aminophenol; ethylenediamine; butylenediamine; hexamethylenediamine;dihexylenetriamine; diethylenetriamine; triethylenetetraamine;dipropylene triamine; m-phenylene diamine; p-phenylenediamine;aminoethylpiperazine; and the like.

Polycarboxylic acid anhydrides which can be employed as the curing agentinclude the anhydrides of maleic acid, succinic acid, citraconic acid,itaconic acid, and the like. The amount of anhydride as a curing agentis about the stoichiometric quantity or preferably about 0.85 gram moleof anhydride carboxyl per one gram mole of epoxy. Of course, this can bevaried as is generally customary in the art.

The flexibilized polymers of this invention can be used as castings;coatings; electrical casting; capsulant and potting compounds; infilament winding; industrial flooring; sealants, e.g. preformed gasketsor they can be applied as a liquid and cured in situ for applicationssuch as sealing the adjacent ends of concrete pavement or sealingwindows within their metal frames; molding resins and toolingcompositions. They can be used for much the same applications as theconventional phenolic based polyepoxide resins and have the advantage offlexibility. Polymeric compositions of this invention can haveelongations which vary over a wide range such as that of over 100% andpreferably over 150 or 200% elongation at break, i.e. the elongation atthe moment of rupture.

The terms oxazolidinone and oxazolidone refer to the same group and areused interchangeably.

The following examples are illustrative of the invention:

EXAMPLE 1 A. A polyether dioxazolidone diepoxide (hereinafter referredto as Product A) was prepared in accordance with the procedure of thisparagraph A. One mole of polypropylene glycol having a molecular weightof about 400 and boron trifiuoride etherate (0.5 ml.) were placed in a1,000 ml. 3-neck flask; controlling the temperature of the reaction atabout 85 C., epichlorohydrin (2 moles) was added dropwise in the flaskto produce the dichlorohydrin of the propylene glycol. After theaddition was complete and no further exotherm developed, the temperaturewas raised to about 95 C. for 30 minutes. The excess catalyst was thenneutralized with calcium oxide. To the above dichlorohydrin there wasadded dichloroethane (300 ml.) and stannous octoate catalyst (0.5 ml.)in a 1,000 ml. 3-neck flask; with stirring there was added tolylenediisocyanate (2,4-2,6-isomers) in a molar ratio of dichlorohydrin totolylene diisocyanate of 2:1. The reaction temperature was controlledbetween about 5 C. and C. for 3 hours and then the temperature wasallowed to climb to room temperature overnight. The condensation productof the tolylene diisocyanate and the dichlorohydrin was thendehydrohalogenated by contact with an aqueous 50% solution of sodiumhydroxide. The dehydrohalogenation temperature was controlled at about70 C. and allowed to run with vigorous stirring for about 2 /2 hours, atwhich time it was cooled and the excess alkali neutralized with carbondioxide. The solids were filtered off and the polyetherdioxazolidonediepoxide, i.e. the di (epoxyalkyl-Z-oxazolidinone)filtrate was concentrated to a syrup having a Brookfield viscosity of2,480 cps. (25 C.), epoxide equivalent weight 600. The preparation of anumber of very similar polyepoxyoxazolidinones are described in U.S.patent application Ser. No. 515,149, filed on Dec. 20, 1965.

B. Product A (28.5 g., 0.045 epoxy equivalent) and Shell 828 1 (28.5 g.,0.15 equiv.) were mixed with 8.6 g. of aminoethylpiperazine. Aftercuring at room temperature for one week this formulation showed:

Tensile=3,000 p.s.i. Elongation at break=67% (ASTM D412, 2 inches perminute) C. Dilution with 10% phenyl glycidyl ether: A panel was preparedfrom Product A (38 g.), Shell 828 (38 g.) phenyl glycidyl ether (7.5 g.;10% by weight of resin content) and aminoethylpiperazine (13.5 g.).After curing at room temperature for one week, tensile:2,950

p.s.i.; elongation at break: 104%.

1 Diglycitlyl ether of Bisphenol A sold by the Shell Chemical Company.

D. Dilution with 10% monoglycidyl ether of polyethylene glycol 300: Apanel was prepared from Product A (38 g.), Shell 828 (38 g.),monoglycidyl ether of polyethylene glycol 300 (7.5 g., 10% by weight ofresin content) and 12.2 g. of aminoethylpiperazine.

After curing at room temperature for one Week, tensile= 1,900 p.s.i.;elongation at break: 108%.

E. Dilution with allyl glycidyl ether: A panel was prepared from ProductA (30 g.), Shell 828 (30 g.), allyl glycidyl ether (7.5 g.; 12.5% ofresin content) and 11.7 g. of aminoethylpiperazine. After curing at roomtemperature for one week, tensile= 1,650 p.s.i.; elongation atbreak=158%.

F. Dilution with glycidyl ether of C C alcohol: 2 A panel was preparedfrom Product A (51 g.), Shell 828 (38 g.), glycidyl ether of C -Calcohol (9 g.) and 15 g. of aminoethylpiperazine. After curing at roomtemperature for one week, the tensile strength of a specimen was 2,200p.s.i., and elongation at break was 177%. Two similar experiments weremade wherein the Product A was left out of the formulation. When theShell 828 resin and the glycidyl ether of C C alcohol was used in equalquantities (without Product A) a very soft resin was produced withlittle strength; also, when the ratio of Shell 828 to the monoglycidylether was 3:1, a resin resulted with very little elongation.

EXAMPLE 2 Fifty grams of Product A of Example 1 was mixed thoroughly bystirring with 50 g. of the mixture of monoglycidyl ethers from octanoland decanol. This mixture had an oxirane oxygen content of 4.95%. Thisflexibilizer mix was added to g. of Epon 828 (Shell Chemical Co),stirred thoroughly, and then degassed under vacuum. To this mixturethere was added 36.1 g. of N-aminoethylpiperazine and the mixture wasstirred at moderate speed to prevent the formation of air bubbles for atime interval of less than 5 minutes. This mixture was then poured intomold designed to give a sheet of /s" thickness. The sample was cured inthe mold for two days in an environment of 23 C. and 50% relativehumidity. The casting was then removed from the mold and allowed to curefor an additional 5 days (total cure =7 days) in the same environment.The properties of the cast sheet were then measured after this roomtemperature cure and after heat aging for 48 additional hours at C. Theresults are tabulated below:

7 Day RT Cure Property 7 Day RT Cure Plus 48 hrs. at

Tensile, max., p.s.i 1, 350 2, 275 Elong. at break, percent 297 161Shore D Hardness 55-40 70-60 What is claimed is: 1. A polymerizablecomposition comprising: (a) A polyepoxyoxazolidinone of the formulaCs-Cm alcohol is a mixture of alkanols having 8 to 10 carbon atoms.

(c) a monoepoxy flexibilizer selected from the group consisting of (i) amonoepoxy compound of the formula wherein R is hydrocarbyl having from 6to about 16 carbon atoms, said hydrocarbyl being a member selected fromthe group consisting of phenyl, alklphenyl and alkyl,

(ii) a monoglycidyl ether of a poly(oxyalkylene)glycol having amolecular weight of 150 to 1000, and

(iii) allyl glycidyl ether; and wherein said composition contains fromabout 0.2 to 4 parts, by weight, of the polyepoxyoxazolidinone for eachpart of the polyglycidyl ether of polyhydric phenol and from about 3% to70% of the monoepoxy fiexibilizer based on the total weight of thepolyepoxyoxazolidinone and polyglyc idyl ether of polyhydric phenol inthe composition.

2. A polymerized composition of claim 1 prepared by contacting saidcomposition with an epoxy curing agent in an amount sutficient to effectcross-linking, said curing agent selected from the group consisting of apolyfunctional amine having at least 2 active amino hydrogen atoms andan aliphatic polycarboxylic acid anhydride.

3. A polymerized composition of claim 2 wherein the curing agent is anamine having at least 2 amino hydrogen atoms.

4. A polymerized composition of claim 3 wherein the monoepoxide is amember selected from the group consisting of phenyl glycidyl ether andthe glycidyl ether of an alkanol having from 6 to 16 carbon atoms.

5. A polymerizable composition comprising:

(a) a polyepoxyoxazolidinone compound of formula:

the

wherein A is the organic residue of a diisocyanate, R a member selectedirom alkylene and chloro-substituted alkylene having from 1 to 4 carbonatoms, n is an integer representing repeating units of said (OR) groups,said (OR) groups having a total molecular weight of from about 150 to1000;

(b) a polyglycidyl ether of a polyhydric phenol selected from the groupconsisting of an epoxylated novolac and a diglycidyl ether ofisopropylidene bis(4- hydroxyphenyl) 8 (c) a monoepoxy compound of theformula wherein R is hydrocarbyl having from 6 to about 16 carbon atomssaid hydrocarbyl being a member selected from the group consisting ofphenyl, alkphenyl and alkyl; and

(d) said composition containing from about 0.3 to

1 part, by weight, of the polyepoxyoxazolidinone for each part of thepolyglycidyl ether of a polyhydric phenol and from about 5% to of themonoepoxy compound based on the weight of the polyepoxyoxazolidinone andpolyglycidyl ether of a polyhdric phenol.

6. A polymerized composition of claim 5 including an amine curing agentfor epoxy compounds said amine having at least two amino hydrogen atoms,wherein R in said (OR) group is propylene, A is tolylene and wherein thesaid polyepoxyoxazolidinone is a liquid.

7. A polymerized composition of claim 6 wherein the amine catalyst isaminoethylpiperazine.

8. A composition of claim 7 wherein the monoepoxy compound is of theformula R OOH -OH-OHg wherein R is alkyl of 8 to 10 carbon atoms.

9. A polymerizable composition comprising: (a) a diepoxyoxazolidinone,normally in the liquid state, of the formula:

wherein A is tolylene, R is propylene and n represents repeating unitsof the (OR) oxypropylene p;

(b) the diglycidyl ether of isopropylidene bis(4-hydroxyphenyl); and

(c) a monoglycidyl ether of an alkanol having 8 to 10 carbon atoms, saidcomposition containing from about 0.3 to 1 part by weight of thepolyepoxyoxazolidinone for each part of the diglycidyl ether ofisopropylidene bis(4-hydroxyphenyl) and from about 15% about to 45% ofthe monoglycidyl ether of said alkan-ol based on the total weight of thepolyepoxyoxazolidinone and the diglycidyl ether of isopropylidenebis(4-hydroxyphenyl).

10. A polymerized composition of claim 9 having an elongation at breakof at least 200%.

No references cited.

MURRAY TILLMAN, Primary Examiner.

PAUL LIEBERMAN, Assistant Examiner.

